Proton exchange composite membrane

ABSTRACT

A proton exchange composite membrane (PECM) and a method of synthesizing the membrane are disclosed. The PECM may include a PBI membrane doped with an acid, an imidazolium-based dicationic ionic liquid, and a mesoporous material. This PECM can be used as an improved high-temperature polymer electrolyte membrane (HT-PEM) fuel cell. The disclosed fuel cell can provide improved proton conductivity, acid uptake, and thermal stability.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of priority from pending U.S.Provisional Patent Application Ser. No. 62/435,897, filed on Dec. 19,2016, and entitled “PROTON EXCHANGE COMPOSITE MEMBRANES AND APPLICATIONSTHEREOF IN HIGH TEMPERATURE PROTON EXCHANGE MEMBRANE FUEL CELLS,” whichis incorporated herein by reference in its entirety.

TECHNICAL FIELD

The present disclosure generally relates to proton exchange compositemembranes, and particularly to methods for preparation of protonexchange composite membranes and applications thereof inhigh-temperature proton exchange membrane fuel cells.

BACKGROUND

Development of membranes for high-temperature polymer electrolytemembrane (HT-PEM) fuel cells under anhydrous conditions may permithigher operating voltages at higher temperatures. Polybenzimidazole(PBI) doped with acids may be used as an electrolyte in HT-PEM fuelcells. Phosphoric acid (PA) may be used for doping PBI to obtain aPA-doped PBI (PA-PBI). However, in PA-PBI membranes, dehydration of PAat temperatures above 150° C. may result in a decrease in protonconductivity. In order to overcome this limitation, ionic liquids may beincorporated into a PBI membrane under anhydrous conditions. Ionicliquids have several characteristics such as high ionic conductivity,electrochemical stability, and thermal stability at higher temperatures(>150° C.) that make them good candidates for being used as anelectrolyte in HT-PEM fuel cells.

PBI composite membranes may be prepared by incorporation of ionicliquids containing imidazolium cations into PBI membranes. Incorporationof ionic liquids containing imidazolium cations into PBI membranes mayincrease the thermal stability and proton conductivity of PBI membraneunder anhydrous conditions. However, in long-term fuel cell operations,the dragging of ionic liquids by water molecules and ionic liquidleakages may be disadvantageous. Mesoporous materials such as orderedmesoporous silica may be used as a diffusional barrier to preventgradual ionic liquid leakage or dragging during long-term operation ofHT-PEM fuel cells. However, there remains a need for a process ofsynthesizing HT-PEMs with improved proton conductivity, acid uptake, andthermal stability, providing improved performance of HT-PEM fuel cells.

SUMMARY

This summary is intended to provide an overview of the subject matter ofthe present disclosure, and is not intended to identify essentialelements or key elements of the subject matter, nor is it intended to beused to determine the scope of the claimed implementations. The properscope of the present disclosure may be ascertained from the claims setforth below in view of the detailed description below and the drawings.

In one general aspect, the present disclosure is directed to a protonexchange composite membrane is disclosed that may include a PBI membranedoped with an acid, an imidazolium-based dicationic ionic liquid, wherea molar ratio of the PBI to the imidazolium-based dicationic ionicliquid is between 2:1 and 11:1, and a mesoporous material, where themesoporous material is present at an amount ranging between 2 and 11percent of a total weight of the PBI.

The above general aspects may have one or more of the followingfeatures. For example, the imidazolium-based dicationic ionic liquid caninclude anions such as CH₃CO₂, CH₃SO₄, C(CF₃SO₂)₂, (Tf₂N) N(CF₃SO₂)₂,(TfO) CF₃SO₂, BF₄, PF₆, ASF₆, SbF₆, CF₃CO₂, or AlCl₄. According to someimplementations, the imidazolium-based dicationic ionic liquid may be1,3-di(3-methylimidazolium) propane bis (trifluoromethylsulfonyl) imide,1,6-di(3-methylimidazolium) hexane bis (hexafluorophosphate), 1,5 bis(3-benzyl-2-methyimidazolium) pentane di-bis (trifloromethanesulfonyl)imide, 1,5 bis (3-methyl-2-phenylimidazolium) pentane di-bis(trifloromethanesulfonyl) imide, 1,5 bis (2,3-dimethylimidazolium)pentane di-bis (trifloromethanesulfonyl) imide, 1,10 bis(2,3-methylimidazolium) decane di-bis (trifluoromethanesulfonyl) imide,1,10 bis (2,3-dimethylimidazolium) decane di-bis(trifluoromethanesulfonyl) imide, or combinations thereof. In otherimplementations, the imidazolium-based dicationic ionic liquid may be1,3-di(3-methylimidazolium) propane bis (trifluoromethylsulfonyl) imide,1,6-di(3-methylimidazolium) hexane bis (hexafluorophosphate), orcombinations thereof. In some cases, the mesoporous material may beSBA-15, SBA-16, MCM-41, or MCM-48. In another example, the mesoporousmaterial may be a modified mesoporous material such as mesoporous SBA-15silica sulfonic acid or mesoporous SBA-15 silica phenyl sulfonic acid.According to one implementation, the acid may be phosphoric acid. Insome cases, the proton exchange composite membrane has an activationenergy ranging between 14 and 21 kJ. In another example, a tensilestrength of the proton exchange composite membrane ranges betweenapproximately 18 and 34 MPa. In some implementations, the currentdensity of the proton exchange composite membrane ranges betweenapproximately 0.6 and 1.2 A/cm² at 0.5 V and 180° C. As another example,a power density of the proton exchange composite membrane can rangebetween approximately 0.3 and 0.6 W/cm² at 0.5 V and 180° C.

In another general aspect, the present disclosure is directed to amethod for synthesizing a proton exchange composite membrane. The methodmay include one or more of the following steps: preparing a PBI solutionby dissolving PBI powder in a solvent, and adding an imidazolium-baseddicationic ionic liquid to the PBI solution to obtain a second solution.A molar ratio of the PBI to the imidazolium-based dicationic ionicliquid can be between 2:1 and 11:1. The method further includesdispersing a mesoporous material in the second solution to obtain athird solution, where the mesoporous material is present at an amountranging between 2 and 11 percent of a total weight of the PBI. Themethod may further include casting the third solution, removing thesolvent from the third solution to obtain a composite membrane, anddoping the composite membrane with phosphoric acid. Theimidazolium-based dicationic ionic liquid includes anions selected fromthe group consisting of CH₃CO₂, CH₃SO₄, C(CF₃SO₂)₂, (Tf₂N) N(CF₃SO₂)₂,(TfO) CF₃SO₂, BF₄, PF₆, ASF₆, SbF₆, CF₃CO₂, and AlCl₄.

The above general aspects may have one or more of the followingfeatures. For example, the imidazolium-based dicationic ionic liquid canbe selected from the group consisting of 1,3-di(3-methylimidazolium)propane bis (trifluoromethylsulfonyl) imide, 1,6-di(3-methylimidazolium)hexane bis (hexafluorophosphate), 1,5 bis (3-benzyl-2-methyimidazolium)pentane di-bis (trifloromethanesulfonyl) imide, 1,5 bis(3-methyl-2-phenylimidazolium) pentane di-bis (trifloromethanesulfonyl)imide, 1,5 bis (2,3-dimethylimidazolium) pentane di-bis(trifloromethanesulfonyl) imide, 1,10 bis (2,3-methylimidazolium) decanedi-bis (trifluoromethanesulfonyl) imide, 1,10 bis(2,3-dimethylimidazolium) decane di-bis (trifluoromethanesulfonyl) imideand combinations thereof. In another example, the imidazolium-baseddicationic ionic liquid is selected from the group consisting of1,3-di(3-methylimidazolium) propane bis (trifluoromethylsulfonyl) imide,1,6-di(3-methylimidazolium) hexane bis (hexafluorophosphate), andcombinations thereof. In some implementations, the mesoporous materialis selected from the group consisting of SBA-15, SBA-16, MCM-41, andMCM-48. In other implementations, the mesoporous material is selectedfrom the group consisting of mesoporous SBA-15 silica sulfonic acid andmesoporous SBA-15 silica phenyl sulfonic acid. In some cases, doping thecomposite membrane includes using a phosphoric acid. As an example, thecomposite membrane may be doped with phosphoric acid at a concentrationof 85 wt % over approximately 5 days. In one implementation, casting thethird solution includes casting onto glass plates by a film applicator.

Other systems, methods, features and advantages of the implementationswill be, or will become, apparent to one of ordinary skill in the artupon examination of the following figures and detailed description. Itis intended that all such additional systems, methods, features andadvantages be included within this description and this summary, bewithin the scope of the implementations, and be protected by thefollowing claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawing figures depict one or more implementations in accord withthe present teachings, by way of example only, not by way of limitation.In the figures, like reference numerals refer to the same or similarelements.

FIG. 1 depicts a method for synthesizing a composite proton exchangemembrane according to one or more implementations of the presentdisclosure;

FIG. 2 illustrates a structure of 1,3-di(3-methylimidazolium) propanebis (trifluoromethylsulfonyl) imide and a structure of1,6-di(3-methylimidazolium) hexane bis (hexafluorophosphate);

FIG. 3 presents an attenuated total reflection Fourier transforminfrared spectroscopy (ATR-FTIR) spectra of mesoporous SBA-15-Ph-SO₃Hand four composite membranes of SBA₁₁-PDC₃₄, SBA₉-PDC₆₄, SBA₉-PMC₆₃ andSBA₄-PMC₄₃, according to one or more implementations of the presentdisclosure;

FIG. 4 is a proton conductivity plot of SBA_(y)-PPDC₃₄ andSBA_(y)-PPMC₆₃ composite membranes and PA-PBI, PPDC₃₄ and PPMC₆₃composite membranes versus SBA-15-Ph-SO₃H content, according to oneimplementation of the present disclosure;

FIG. 5 presents scanning electron microscope with energy dispersiveX-ray spectroscope (SEM-EDX) images of SBA₁₁-PDC₃₄ and SBA₁₅-PDC₃₄,according to one implementation of the present disclosure;

FIG. 6 shows SEM-EDX images of SBA₉-PMC₆₃ and SBA₁₃-PMC₆₃, according toone implementation of the present disclosure;

FIG. 7 shows PA_(dop) versus SBA-15-Ph-SO₃H content plots ofSBA_(y)-PPDC₃₄, SBA_(y)-PPMC₆₃, PA-PBI, PPDC₃₄, and PPMC₆₃ compositemembranes, according to one or more implementations of the presentdisclosure;

FIG. 8 is a proton conductivity plot of SBA_(y)-PPDC₆₄, SBA_(y)-PPMC₄₃,PA-PBI, PPDC₆₄, and PPMC₄₃ composite membranes versus SBA-15-Ph-SO₃Hcontent, according to one or more implementations of the presentdisclosure;

FIG. 9 shows SEM-EDX images of SBA₉-PDC₆₄ and SBA₁₃-PDC₆₄, according toone implementation of the present disclosure;

FIG. 10 shows SEM-EDX images of SBA₇-PMC₄₃ and SBA₁₁-PMC₄₃, according toone implementation of the present disclosure;

FIG. 11 shows PA_(dop) versus SBA-15-Ph-SO₃H content plots ofSBA_(y)-PPDC₆₄, SBA_(y)-PPMC₄₃, PA-PBI, PPDC₆₄, and PPMC₄₃ compositemembranes, according to one or more implementations of the presentdisclosure;

FIG. 12A shows Arrhenius plots of SBA₁₁-PPDC₃₄ and SBA₉-PPMC₆₃ compositemembranes, according to one implementation of the present disclosure;

FIG. 12B shows Arrhenius plots of SBA₉-PPDC₆₄ and SBA₇-PPMC₄₃ compositemembranes, according to one implementation of the present disclosure;

FIG. 13A shows time stability plot of proton conductivity forSBA₁₁-PPDC₃₄ and SBA₉-PPMC₆₃ at 180° C., according to one implementationof the present disclosure;

FIG. 13B shows time stability plot of proton conductivity forSBA₉-PPDC₆₄ and SBA₇-PPMC₄₃ at 180° C., according to one implementationof the present disclosure;

FIG. 14A shows mechanical stability plots for SBA_(y)-PPDC₃₄ compositemembrane, according to one implementation of the present disclosure;

FIG. 14B shows mechanical stability plots for SBA_(y)-PPMC₆₃ compositemembrane, according to one implementation of the present disclosure;

FIG. 15A shows mechanical stability plots for SBA_(y)-PPDC₆₄ compositemembrane, according to one implementation of the present disclosure;

FIG. 15B shows mechanical stability plots for SBA_(y)-PPMC₄₃ compositemembrane, according to one implementation of the present disclosure;

FIGS. 16A-16C show polarization curves of SBA₁₁-PPDC₃₄ and SBA₉-PPMC₆₃composite membranes in the temperature range of 80-180° C., according toone implementation of the present disclosure;

FIG. 16D-16F show polarization curves of SBA₉-PPDC₆₄ and SBA₇-PPMC₄₃composite membranes in the temperature range of 80-180° C., according toone implementation of the present disclosure;

FIG. 17 shows polarization curves for Nafion 117 membrane at 80° C., 90°C., 100° C. and 120° C., according to one implementation of the presentdisclosure;

FIG. 18A shows power density plots of PPDC₃₄, PPMC₆₃, SBA₁₁-PPDC₃₄,SBA₉-PPMC₆₃ composite membranes along with power density plots of Nafionand PA-PBI at 0.5 V, according to one implementation of the presentdisclosure;

FIG. 18B shows power density plots of PPDC₆₄, PPMC₄₃, SBA₉-PPDC₆₄,SBA₇-PPMC₄₃ composite membranes along with power density plots of Nafionand PA-PBI at 0.5 V, according to one implementation of the presentdisclosure;

FIG. 19A shows a life test result of PPDC₃₄ membrane unit cell operatedat 180° C. under a constant current loading of 0.4 A/cm², according toone implementation of the present disclosure; and

FIG. 19B shows a life test result of SBA₁₁-PPDC₃₄ membrane unit celloperated at 180° C. under a constant current loading of 0.4 A/cm²,according to one implementation of the present disclosure.

DETAILED DESCRIPTION

The following detailed description is presented to enable a personskilled in the art to make and use the methods and devices disclosed inexemplary embodiments of the present disclosure. For purposes ofexplanation, specific nomenclature is set forth to provide a thoroughunderstanding of the present disclosure. However, it will be apparent toone skilled in the art that these specific details are not required topractice the disclosed exemplary embodiments. Descriptions of specificexemplary embodiments are provided only as representative examples.Various modifications to the exemplary implementations will be readilyapparent to one skilled in the art, and the general principles definedherein may be applied to other implementations and applications withoutdeparting from the scope of the present disclosure. The presentdisclosure is not intended to be limited to the implementations shown,but is to be accorded the widest possible scope consistent with theprinciples and features disclosed herein. In the following detaileddescription, numerous specific details are set forth by way of examplesin order to provide a thorough understanding of the relevant teachings.However, it should be apparent that the present teachings may bepracticed without such details. In other instances, well known methods,procedures, components, and/or circuitry have been described at arelatively high-level, without detail, in order to avoid unnecessarilyobscuring aspects of the present teachings.

The following disclosure describes a composite proton exchange membraneand a method for preparing the composite proton exchange membrane, wherethe membrane may include polybenzimidazole (PBI) doped with an acid, adicationic ionic liquid including imidazolium cations, and a mesoporousmaterial.

In order to provide the reader with an overview, FIG. 1 illustrates amethod 100 for synthesizing a composite proton exchange membraneaccording to one or more implementations of the present disclosure. Inone implementation, the method 100 may include a first step 101 ofpreparing a PBI solution by dissolving PBI powder in a solvent; a secondstep 102 of adding a dicationic ionic liquid to the PBI solution toobtain a second solution; a third step 103 of dispersing a mesoporousmaterial in the second solution to obtain a third solution; a fourthstep 104 of casting the third solution; a fifth step 105 of removing thesolvent from the third solution to obtain a composite membrane; and asixth step 106 of doping the composite membrane with an acid. Additionaldetails regarding these steps are provided below.

With respect to the first step 101, in some implementations, thepreparation of the PBI solution may involve dissolving the PBI powder inan organic solvent such as dimethylacetamide (DMAc) under a nitrogenatmosphere at a temperature of approximately 150° C. According to oneimplementation, the PBI solution may have a concentration of at least 2wt %.

Furthermore, in some implementations, in the second step 102 of method100, a dicationic ionic liquid (IL) may be added to the PBI solution toobtain a second solution containing PBI and the dicationic ionic liquidwith a PBI to IL molar ratio between 2:1 and 9:1.

According to one implementation, the addition of dicationic IL to thePBI solution may be followed by rigorous stirring at a temperature ofapproximately 35° C. for a predetermined amount of time, for example 24h.

With respect to the second step 102, according to some implementations,the dicationic IL may be a dicationic IL that includes imidazoliumcations. A dicationic IL that includes imidazolium cations is referredto herein as imidazolium-based dicationic IL. The imidazolium-baseddicationic IL may have different anions such as CH₃CO₂, CH₃SO₄,C(CF₃SO₂)₂, (Tf₂N) N(CF₃SO₂)₂, (TfO) CF₃SO₂, BF₄, PF₆, ASF₆, SbF₆,CF₃CO₂, AlCl₄ and the like. For example, the imidazolium-based IL may be1,3-di(3-methylimidazolium) propane bis (trifluoromethylsulfonyl) imide,1,6-di(3-methylimidazolium) hexane bis (hexafluorophosphate), 1,5 bis(3-benzyl-2-methyimidazolium) pentane di-bis (trifloromethanesulfonyl)imide, 1,5 bis (3-methyl-2-phenylimidazolium) pentane di-bis(trifloromethanesulfonyl) imide, 1,5 bis (2,3-dimethylimidazolium)pentane di-bis (trifloromethanesulfonyl) imide, 1,10 bis(2,3-methylimidazolium) decane di-bis (trifluoromethanesulfonyl) imide,1,10 bis (2,3-dimethylimidazolium) decane di-bis(trifluoromethanesulfonyl) imide or a combination thereof.

In addition, according to some implementations, the third step 103 mayinvolve dispersing a mesoporous material such as mesoporous silica inthe second solution to obtain a third solution. For example, amesoporous silica such as SBA-15, SBA-16, MCM-41, or MCM-48 may bedispersed in the second solution. According to one implementation,functionalized mesoporous silica, such as mesoporous SBA-15 silicasulfonic acid or mesoporous SBA-15 silica phenyl sulfonic acid(SBA-15-Ph-SO₃H) may be dispersed in the second solution with, forexample, an ultrasonic probe. According to some implementations, themesoporous material may be dispersed in the second solution with aweight percent of mesoporous material/PBI between about 5 and 15.

With respect to fourth step 104, in one implementation, the thirdsolution may be cast or otherwise coated on a glass plate using a filmapplicator to form a thin film of the third solution. In fifth step 105,in some implementations, the solvent in the thin film of the thirdsolution may be removed by heating the film of the third solution andthereby evaporating the solvent. According to one implementation, thethin film of the third solution may be heated at a temperature ofapproximately 80° C. for about 16 h and then at a temperature of 120° C.for 5 h under vacuum in order to remove the solvent and obtain thecomposite membrane.

Referring again to FIG. 1, according to one implementation, afterremoving the solvent from the third solution and obtaining the compositemembrane, method 100 may proceed to the sixth step 106. In someimplementations, the sixth step 106 may involve doping the compositemembrane with an acid such as phosphoric acid for a predetermined amountof time to obtain the composite proton exchange membrane of the presentdisclosure. According to one implementation, the composite membrane maybe doped with phosphoric acid with a concentration of about 85% foraround 5 days.

In some implementations, the composite proton exchange membrane that maybe synthesized as described in detail in connection with method 100 ofFIG. 1 may include PBI doped with phosphoric acid, an imidazolium-baseddicationic IL, and a functionalized mesoporous silica. Animidazolium-based dicationic IL includes two singly charged imidazoliumcations that are linked by an alkyl chain spacer and are paired with twosingly charged anions.

For example, FIG. 2 illustrates a structure 201 of1,3-di(3-methylimidazolium) propane bis (trifluoromethylsulfonyl) imide(referred to herein as DC₃) and a structure 202 of1,6-di(3-methylimidazolium) hexane bis (hexafluorophosphate) (referredto herein as DC₆). In FIG. 2, structure 201 includes two singly chargedimidazolium cations 204 that are linked by an alkyl chain spacer 205 tocompose a doubly charged cation 203. The two singly charged imidazoliumcations 204 are paired with two singly charged Bis(trifluoromethanesulfonyl) imide (Tf₂N) anions 206 to form the DC₃ ionicliquid. With further reference to FIG. 2, structure 202 also includestwo singly charged imidazolium cations 204 that are linked by an alkylchain spacer 207 to compose a doubly charged cation 208. The two singlycharged imidazolium cations 204 are paired with two singly charged bis(hexafluorophosphate) (PF₆) anions 209 to form the DC₆ ionic liquid. Itshould be understood that the imidazolium-based dicationic IL mayinclude different anions such as CH₃CO₂, CH₃SO₄, C(CF₃SO₂)₂, (Tf₂N)N(CF₃SO₂)₂, (TfO) CF₃SO₂, BF₄, PF₆, ASF₆, SbF₆, CF₃CO₂, AlCl₄ and thelike.

In some implementations, the composite proton exchange membrane that maybe synthesized as described in detail in connection with method 100 ofFIG. 1 may have a general formula of SBA_(y)-(PA-PBI) DCIL_(x), whereSBA represents the functionalized mesoporous silica. In differentimplementations, the functionalized mesoporous silica may be for examplea mesoporous SBA-15 silica sulfonic acid or a mesoporous SBA-15 silicaphenyl sulfonic acid. PA-PBI represents the PBI doped with phosphoricacid and DCIL represents the imidazolium-based dicationic IL. In theformula, y is weight ratio of functionalized mesoporous silica to PBIand x is mole ratio of PBI/IL. According to one implementation, y mayhave a value between about 5 and 15 and x may have a value between about2 and 9.

Example

In the following example, four different composite proton exchangemembranes were synthesized by the method 100 of FIG. 1. SBA-15-Ph-SO₃Hwere used as the functionalized mesoporous silica and two types ofdicationic ionic liquids DC₃, DC₆, as well as two types of monocationicionic liquids 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl)imide (referred to herein as MC₆) and 1-butyl-3-methylimidazoliumhexafluorophosphate) (referred to herein as MC₄) were used as the ionicliquid for synthesizing the four different composite proton exchangemembranes.

In order to synthesize the composite proton exchange membranes, PBIpowder was first dissolved in DMAc under a nitrogen atmosphere at 150°C. to obtain a PBI solution with a concentration of 2 wt %. Then DC₃,DC₆, MC₄, and MC₆ ionic liquids were added to the PBI solutions in fourseparate containers to obtain four different second solutions. The foursecond solutions were vigorously stirred for approximately 24 hours at35° C. Following this step, different amounts of mesoporousSBA-15-Ph-SO₃H were dispersed in the four second solutions using anultrasonic bath. The obtained solutions were then directly cast ontoglass plates by a film applicator. The cast solutions were heated at 80°C. for approximately 16 hours and then at 120° C. for 5 hours undervacuum to remove DMAc solvent to obtain four membranes SBA_(y)-PDC_(3x),SBA_(y)-PDC_(6x), SBA_(y)-PMC_(6x) and SBA_(y)-PMC_(4x). The obtainedfour membranes were then doped with phosphoric acid (PA) with aconcentration of 85 wt % for approximately 5 days to obtain dopedcomposite membranes that are referred to herein as SBA_(y)-PPDC_(3x),SBA_(y)-PPDC_(6x), SBA_(y)-PPMC_(6x) and SBA_(y)-PPMC_(4x). Here, xrepresents mole ration of PBI/ionic liquid. In this example, fordicationic ionic liquids DC₃ and DC₆, x is chosen to be 4 and formonocationic ionic liquids MC₄ and MC₆, x is chosen to be 3.Furthermore, y represents weight ratio of PBI/mesoporous SBA-15-Ph-SO₃H.Consequently, the obtained composite membranes before doping with PA arereferred to as SBA₁₁-PDC₃₄, SBA₉-PDC₆₄, SBA₉-PMC₆₃ and SBA₇-PMC₄₃, anddoped composite membranes in this example are referred to asSBA₁₁-PPDC₃₄, SBA₉-PPDC₆₄, SBA₉-PPMC₆₃ and SBA₇-PPMC₄₃.

Referring now to FIG. 3, attenuated total reflection Fourier transforminfrared spectroscopy (ATR-FTIR) spectra of mesoporous SBA-15-Ph-SO₃Hand four composite membranes of SBA₁₁-PDC₃₄, SBA₉-PDC₆₄, SBA₉-PMC₆₃ andSBA₇-PMC₄₃ are shown. The presence of sulfonic acid group in thecomposite membranes may be confirmed by the absorption bands assigned tothe sulfonic acid group at 1145 cm⁻¹ (asymmetric O═S—O stretch), 1030cm⁻¹ (S═O stretch), and 830 cm⁻¹ (S—O stretch). The 1050 and 800 cm⁻¹regions correspond to Si—O—Si and Si—O—Si stretching of the silicatenetwork, respectively. The peak at 880-920 cm⁻¹ corresponds to the Si—OHstretching vibration of the hydrogen-bonded silanol groups in SBA-15.The peaks of single substituted phenyl group also appear at 740 and 700cm⁻¹, respectively. The band at 1000-1250 cm-1 may be attributed to thestretching of the Tf₂N anion in composite membranes. The peak around1445 cm⁻¹ may suggest deformation of benzimidazole “Breathing” mode ofimidazole rings of the PBI membrane. The peak at 1600 cm⁻¹ may beassigned to the C═C and C═N stretching groups and the peak at 2900 cm⁻¹may be assigned to the stretching vibration of aromatic C—H groups.

The proton conductivities of the composite membranes were evaluated byin-plane measurements using four-point-probe AC impedance spectroscopy.Measurements were carried out with a PGSTAT303N potentiostat/galvanostat(Ecochemie) with a frequency range of 100 Hz to 1 MHz and voltageamplitude of 50 mV. Temperature was controlled using a Globe TechComputer Cell GT fuel cell test station. It is generally believed thatthe in-plane conductivity measurements are easier to carry out andprovide greater accuracy due to the larger cell constant, L/A, where Lis the distance between electrodes, usually several millimeters, and Ais the cross-sectional area of the sample. Conductivity measurements ofDC₆ and MC₄ ILs in PA solution (Purity: 85%) were carried out usingThermo Fisher Scientific/Eutech Instrument PC700 pH/mV/Conductivitymeter.

FIG. 4 is a proton conductivity plot of SBA_(y)-PPDC₃₄ andSBA_(y)-PPMC₆₃ composite membranes and PA-PBI, PPDC₃₄ and PPMC₆₃composite membranes versus SBA content which is represented by y. PA-PBIis a PBI membrane doped with PA, PPDC₃₄ and PPDC₆₃ are compositemembranes containing dicationic ionic liquids DC₃ and DC₄ to which nomesoporous silica were added.

As shown in FIG. 4, proton conductivity of PA-PBI membrane was 3.1 mS/cmin 25° C. The SBA₁₁-PPDC₃₄ and SBA₉-PPMC₆₃ composite membranes displayeda higher proton conductivity compared to the PA-PBI membranes. Thisimprovement may be attributed to the hygroscopic nature and high surfacearea of mesoporous SBA-15-Ph-SO₃H. Presence of highly hydrophilicmesoporous SBA-15-Ph-SO₃H within the matrix of the composite membranesmay increase the PA uptake ability of composite membranes to a higheramount compared to that of PBI membranes. High surface area ofSBA-15-Ph-SO₃H mesoporous provides hydrogen bond interactions betweenmesoporous silica, ionic liquids, PA and PBI in composite membranes. Thepore size of SBA-15-Ph-SO₃H mesoporous is 4.8 nm and may play arelatively important role in increasing the proton conductivity ofcomposite membranes. The SBA_(y)-PPDC₃₄ composite membranes demonstratedhigher conductivity in comparison with SBA_(y)-PPMC₆₃ compositemembranes. This result may be attributed to high interactions of DC₃ionic liquid and mesoporous SBA-15-Ph-SO₃H. Mesoporous SBA-15-Ph-SO₃Hmay make strong and effective hydrogen bond interactions with highcharge density of DC₃ ionic liquid. The SBA₁₁-PPDC₃₄ composite membranedisplayed the highest conductivity (47 mS/cm) in comparison with othercomposite membranes. Increasing the mesoporous SBA-15-Ph-SO₃H content inSBA_(y)-PPDC₃₄ and SBA_(y)-PPMC₆₃ composite membranes (a y>1 forSBA_(y)-PPDC₃₄ and a y>9 for SBA_(y)-PPMC₆₃) decreases the protonconductivity of composite membranes. These results can be attributed tothe self-aggregation of the SBA-15-Ph-SO₃H mesoporous inside thecomposite membranes.

FIG. 5 shows scanning electron microscope with energy dispersive X-rayspectroscope (SEM-EDX) images 501 and 502 of SBA₁₁-PDC₃₄ and SEM-EDXimages 503 and 504 of SBA₁₅-PDC₃₄. Referring to image 502, mesoporousSBA-15-Ph-SO₃H has a homogenous distribution in the cross-section ofSBA₁₁-PDC₃₄ composite membrane. In contrast, referring to image 504,significant agglomerations of Si particles are noticeably observable inthe SBA₁₅-PDC₃₄ composite membrane. Thus, it can be understood thatimages 502 and 504 support that aggregation of the Si nanoparticleshappens at high content of mesoporous SBA-15-Ph-SO₃H. The self-aggregateof Si particles leads to a decrease in the active surface area of theSBA-15-Ph-SO₃H, and consequently the proton conductivity of the membraneis decreased.

FIG. 6 shows SEM-EDX images 601 and 602 of SBA₉-PMC₆₃ and SEM-EDX images603 and 604 of SBA₁₃-PMC₆₃. Referring to image 602, mesoporousSBA-15-Ph-SO₃H has a homogenous distribution in the cross-section ofSBA₉-PMC₆₃ composite membrane. In contrast, referring to image 604,significant agglomerations of Si particles are noticeably observable inthe SBA₁₃-PMC₆₃ composite membrane. Thus, it can be understood thatimages 602 and 604 support that aggregation of the Si particles happensat high content of mesoporous SBA-15-Ph-SO₃H. The self-aggregate of Siparticles leads to a decrease in the active surface area of theSBA-15-Ph-SO₃H and consequently the proton conductivity is decreased inSBA₁₃-PMC₆₃ in comparison with SBA₉-PMC₆₃.

As mentioned before, the composite membranes SBA₁₁-PPDC₃₄, SBA₉-PPDC₆₄,SBA₉-PPMC₆₃ and SBA₇-PPMC₄₃ were doped with PA by immersion in anaqueous PA solution with a concentration of 85 wt % for 5 days.Afterwards, the composite membranes were dried with a blotting paper andfinally evacuated at 80° C. for at least 24 h. The PA doping level(designated herein by PA_(dop)) of membranes was defined as moles of PAobtained for 1 mol of each repeat unit of PBI, and was calculated usingequation (1) below:

$\begin{matrix}{{PA}_{dop} = \frac{\lbrack {( {W_{1} - W_{0}} )/98} \rbrack}{\lbrack {W_{0}/308} \rbrack}} & {{Equation}\mspace{14mu} (1)}\end{matrix}$

Where W₀ is total weight of a dry composite membrane, W₁ is the weightof a PA-PBI membrane, and the values 98 and 308 are the molecularweights of PA and a PBI repeat unit, respectively.

In FIG. 7, PA_(dop) versus SBA-15-Ph-SO₃H content plots ofSBA_(y)-PPDC₃₄ and SBA_(y)-PPMC₆₃ composite membranes and PA-PBI, PPDC₃₄and PPMC₆₃ composite membranes are shown. Referring to FIG. 7, it can beobserved that by incorporation of ILs and mesoporous SBA-15-Ph-SO₃H incomposite membranes, the PA_(dop) of SBA_(y)-PPDC₃₄ (up to y=11) andSBA_(y)-PPMC₆₃ (up y=9) composite membranes increases. The Ph-SO₃Hgroups of mesoporous SBA-15-Ph-SO₃H and TF₂N anions of DC₃ IL take partin the mechanism of proton transfer and therefore more PA can beabsorbed into the composite membranes. Ordered structure ofSBA-15-Ph-SO₃H mesoporous may increase PA absorption of the compositemembranes. Pores of SBA-15-Ph-SO₃H mesoporous may adsorb more ionicliquids and PA in the composite membrane structure. The SBA₁₁-PPDC₃₄composite membrane shows the highest PA_(dop) (13 mol of PA per mole PBIrepeat unit) at dry condition. The results may indicate that DC₃ ionicliquid has strong hydrogen bond interactions with mesoporousSBA-15-Ph-SO₃H and PA in SBA₁₁-PPDC₃₄ composite membranes which may leadto an increase in PA_(dop) of the SBA₁₁-PPDC₃₄ composite membrane.

FIG. 8 is a proton conductivity plot of SBA_(y)-PPDC₆₄ andSBA_(y)-PPMC₄₃ composite membranes and PA-PBI, PPDC₆₄ and PPMC₄₃composite membranes versus SBA-15-Ph-SO₃H content which is representedherein by y. The SBA_(y)-PPDC₆₄ (up to y=9) and SBA_(y)-PPMC₄₃ (up toy=7) composite membranes showed a high proton conductivity compared withPBI membranes. These results may be attributed to high surface area andpores of mesoporous SBA-15-Ph-SO₃H. The SBA_(y)-PPDC₆₄ compositemembrane reflected higher proton conductivity compared to SBA_(y)-PPMC₄₃composite membrane, due to greater hydrogen bond interaction of DC₆ionic liquid. The imidazolium cations in DC₆ IL have different positionsand numbers of possible hydrogen bonding. The hydrogen bond between theC₂ hydrogen atom (the hydrogen atom attached to the single carbon atombonded to two nitrogen atoms) of an imidazolium cation and PF₆ anion hasbeen regarded as an important interaction in controlling the structuresand physical properties. The nature of this hydrogen bond isconsiderably different from that of conventional hydrogen bonds. Thisinteraction is significantly stronger than conventional hydrogen bonds.The size of hydrogen bond is determined mainly by the distance betweenthe imidazolium ring and the anion. The PF₆ anions in DC₆ IL would makemore hydrogen bond interactions with PA and SBA-15-Ph-SO₃H and so wouldincrease the proton conductivity of SBA_(y)-PPDC₆₄ composite membrane incomparison with SBA_(y)-PPMC₄₃ composite membranes. SBA₉-PPDC₆₄composite membrane showed the highest proton conductivity (39 mS/cm) incomparison with other SBA_(y)-PPDC₆₄ and SBA_(y)-PPMC₄₃ compositemembranes at 25° C.

FIG. 9 shows scanning electron microscope with energy dispersive X-rayspectroscope (SEM-EDX) images 901 and 902 of SBA₉-PDC₆₄ and SEM-EDXimages 903 and 904 of SBA₁₃-PDC₆₄. Referring to image 902, mesoporousSBA-15-Ph-SO₃H has a homogenous distribution in the cross-section ofSBA₉-PDC₆₄ composite membrane. In contrast, referring to image 904,significant agglomerations of Si particles are noticeably observable inthe SBA₁₃-PDC₆₄ composite membrane. Images 902 and 904 show that theaggregation of Si particles happens at high content of mesoporousSBA-15-Ph-SO₃H. The self-aggregate of Si particles leads to a decreasein the active surface area of the SBA-15-Ph-SO₃H and consequently themembrane proton conductivity is decreased.

FIG. 10 shows scanning electron microscope with energy dispersive X-rayspectroscope (SEM-EDX) images 1001 and 1002 of SBA₇-PMC₄₃ and SEM-EDXimages 1003 and 1004 of SBA₁₁-PMC₄₃. Referring to image 1002, mesoporousSBA-15-Ph-SO₃H has a homogenous distribution in the cross-section ofSBA₇-PMC₄₃ composite membrane. In contrast, referring to image 1004,significant agglomerations of Si particles are noticeably observable inthe SBA₁₁-PMC₄₃ composite membrane. Images 1002 and 1004 show that theaggregation of Si particles happens at high content of mesoporousSBA-15-Ph-SO₃H. The self-aggregate of Si particles leads to a decreasein the active surface area of the SBA-15-Ph-SO₃H and consequently themembrane proton conductivity is decreased in SBA₁₁-PMC₄₃ in comparisonwith SBA₇-PMC₄₃.

FIG. 11 shows PA_(dop) versus SBA-15-Ph-SO₃H content plots ofSBA_(y)-PPDC₆₄ and SBA_(y)-PPMC₄₃ composite membranes and PA-PBI, PPDC₆₄and PPMC₄₃ composite membranes. SBA_(y)-PPDC₆₄ composite membranesshowed higher PA_(dop) compared to SBA_(y)-PPMC₄₃ composite membranes.Hydrogen bonds interactions between PA, DC₆ ionic liquid and -Ph-SO₃Hgroups of SBA-15-Ph-SO₃H mesoporous act as a continuous path forabsorption of PA in the SBA_(y)-PPDC₆₄ composite membranes. SBA₉-PPDC₆₄composite membranes showed the highest PA_(dop) (11 mol).

FIG. 12A shows Arrhenius plots of SBA₁₁-PPDC₃₄ and SBA₉-PPMC₆₃ compositemembranes. The SBA₁₁-PPDC₃₄ composite membranes showed higher protonconductivities in different temperatures in comparison with SBA₉-PPMC₆₃composite membranes. The proton conductivity of SBA₁₁-PPDC₃₄ compositemembranes were about 123 mS/cm at 180° C., which may be considered asignificant increase in proton conductivity.

FIG. 12B shows Arrhenius plots of SBA₉-PPDC₆₄ and SBA₇-PPMC₄₃ compositemembranes. The SBA₉-PPDC₆₄ composite membranes displayed high protonconductivity in deferent temperature compared with SBA₇-PPMC₄₃ compositemembranes. The proton conductivity of composite membranes increases withincreasing temperature. An increase in proton conductivity at hightemperatures in composite membranes is due to an increase in transferkinetics with increasing temperature. The lower activation energy forproton transfer can increase proton transfer speed in high-temperature.The pores of SBA-15-Ph-SO₃H mesoporous act as continuous ion channels ofprotons in high temperatures in the presence of dicationic ionicliquids. The proton conductivity of SBA₉-PPDC₆₄ composite membranesobtained 90 mS/cm at 180° C.

Referring to FIGS. 12A and 12B, the activation energies (E_(a)) for theproton transport in composite membranes calculated from the slope of theArrhenius plots, ln(σ) versus 1000/T (K) are presented. Furthermore,Table 1 below reports activation energies of composite membranes. Theactivation energy of cationic dicationic composite membranes(SBA₁₁-PPDC₃₄ and SBA₉-PPDC₆₄) was less than that of monocationiccomposite membranes (SBA₉-PPMC₆₃ and SBA₇-PPMC₄₃). The results showedthat the activation energies for proton transfer in dicationic compositemembranes were less than monocationic composite membranes. As a result,proton transfers speeds were more in dicationic composite membranes.According to Table 1, the activation energies were the range of 14-21kJmol⁻¹ in composite membranes. The results show that the dominantmechanism of composite membranes for proton transfer is the mutationmechanism.

TABLE 1 Activation energies of dicationic and monocationic compositemembranes SBA₁₁- SBA₉- SBA₉- SBA₇- Membrane PPDC₃₄ PPMC₆₃ PPDC₆₄ PPMC₄₃E_(a) 14.13 18.19 16.56 20.15 (kJ/mol)

FIG. 13A shows time stability plot of proton conductivity forSBA₁₁-PPDC₃₄ and SBA₉-PPMC₆₃ at 180° C. and FIG. 13B shows timestability plot of proton conductivity for SBA₉-PPDC₆₄ and SBA₇-PPMC₄₃ at180° C. The proton conductivity of composite membranes was investigatedat 180° C., and it was kept overnight at 150° C. The proton conductivityof composite membranes remained almost constant for the duration of 144hours and very little reduction was observed. This phenomenon is due tothe presence of SBA-15-Ph-SO₃H mesoporous in the structure of compositemembranes. The pores of the SBA-15-Ph-SO₃H mesoporous have an importantrole in the prevention of leaching of ionic liquids in compositemembranes. These pores provide high surface to maintain the ionicliquids and PA in the structure of composite membranes. At hightemperatures, the presence of SBA-15-Ph-SO₃H mesoporous in compositemembranes leads to a significant increase in proton conductivity. Thereason for this view is that the SBA-15-Ph-SO₃H mesoporous providescontinuous path for proton transfer at high temperatures. The -Ph-SO₃Hgroups play an important role in the formation of hydrogen bonds inproton transfer process. SBA₁₁-PPDC₃₄ and SBA₉-PPDC₆₄ dicationiccomposite membranes displayed less reduction of proton conductivitycompared with SBA₉-PPMC₆₃ and SBA₇-PPMC₄₃ monocationic compositemembranes. This can be understood to be a result of the effectivehydrogen bond interactions of dicationic ionic liquid (DC₃ and DC₆) withSBA-15-Ph-SO₃H mesoporous compared with monocationic ionic liquids (MC₆and MC₄) in dicationic composite membranes. The presence SBA-15-Ph-SO₃Hmesoporous in dicationic composite membranes which have a high chargedensity, provides high hydrogen bond interactions for maintain PA andionic liquids.

FIG. 14A shows mechanical stability plots for SBA_(y)-PPDC₃₄ compositemembrane and FIG. 14B shows mechanical stability plots forSBA_(y)-PPMC₆₃ composite membrane. Mechanical stability ofSBA_(y)-PPDC₃₄ and SBA_(y)-PPMC₆₃ composite membranes increased withincorporation of SBA-15-Ph-SO₃H mesoporous. This phenomenon is due tothe hydrogen bond interactions of SBA-15-Ph-SO₃H mesoporous with Ils inthe membrane matrix. SBA-15-Ph-SO₃H mesoporous with high surface tovolume ratio have a greater possibility of interactions with membranematrix.

Referring to FIGS. 14A and 14B, with the addition of SBA-15-Ph-SO₃Hmesoporous in composite membrane, which create hydrogen bonds betweenthe SBA-15-Ph-SO₃H mesoporous, ionic liquids and membrane, the membranestructure became more compact and the mechanical strength and module ofthe membrane was improved. Improving the mechanical strength ofcomposite membranes by increasing hydrogen bonds decreases the amount offreedom and mobility of polymer chains in the membrane. Decreasedmobility of polymer chains in the membranes has a direct impact on theelongation of the membrane. The decreased mobility of polymer chainsfurther causes a reduction of the elongation of the membrane and so themembrane becomes more rigid. The SBA_(y)-PPDC₃₄ composite membranesdisplayed high mechanical stability compared with SBA_(y)-PPMC₆₃composite membranes, which can be understood to result from the highinteractions between SBA-15-Ph-SO₃H mesoporous and DC₃ ionic liquid.Uniform dispersion of SBA-15-Ph-SO₃H mesoporous is an important factorin these interactions. Hence SBA₁₁-PPDC₃₄ composite membranes due tohomogenous dispersion of SBA-15-Ph-SO₃H mesoporous demonstrated highmechanical stability compared with others SBA_(y)-PPDC₃₄ compositemembranes.

FIG. 15A shows mechanical stability plots for SBA_(y)-PPDC₆₄ compositemembrane and FIG. 15B shows mechanical stability plots forSBA_(y)-PPMC₄₃ composite membrane. SBA_(y)-PPDC₆₄ composite membranesbecause of DC₆ ionic liquid interactions displayed high mechanicalstability compared with SBA_(y)-PPMC₄₃ composite membranes. SBA₉-PPDC₆₄composite membranes due to homogenous dispersion of SBA-15-Ph-SO₃Hmesoporous demonstrated high mechanical stability compared with othersSBA_(y)-PPDC₆₄ composite membranes.

Referring to Table 2 below, the mechanical strengths of dicationicmembranes, monocationic membranes, dicationic and monocationic compositemembranes are presented. The strong hydrogen bonding between N and —NH—groups is a key factor controlling the mechanical behavior of the PBI.When ionic liquids are introduced into the PBI structure in dicationicmembranes (PPDC₃₄ and PPDC₆₄) and monocationic membranes (PPMC₆₃ andPPMC₄₃), the molecular cohesion between PBI chains is decreased.However, the hydrogen bonds between nitrogen atoms and DC₃ ionic liquidwould increase the cohesion. As a result of these opposite effects, noimportant change of modulus or tensile strength of the PBI membranes isobserved.

TABLE 2 Mechanical strength of dicationic membranes, monocationicmembranes, and dicationic and monocationic composite membranes. Tensilestrength Modulus Elongation at break Membranes (MPa) (GPa) (%) PA-PBI 140.4 50 PPDC₃₄ 8 0.2 65 SBA₁₁-PPDC₃₄ 34 0.55 23 PPDC₆₄ 7 0.15 67SBA₉-PPDC₆₄ 29 0.5 35 PPMC₆₃ 6 0.14 74 SBA₉-PPMC₆₃ 29 0.45 37 PPMC₄₃ 50.11 78 SBA₇-PPMC₄₃ 18 0.43 41

Dicationic and monocationic composite membranes displayed highmechanical stability compared with dicationic and monocationicmembranes. This result may be attributed to high interface interactionsof SBA-15-Ph-SO₃H mesoporous with membranes matrix in compositemembranes.

The prepared composite membranes and Nafion 117 were used to prepareMEAs. The catalyst was Pt—C(E-TEK, 20 wt % Pt) and the Pt loadings ofanode and cathode were 0.5 mg/cm². The MEA of composite membranes wasfabricated according to the literature procedure [41]:Pt—C/PBI/LiCl/DMAc (3.6/1/0.2/38 by wt) catalyst solution was preparedby ultrasonic disturbing for 1 h. The catalyst ink was painted ontocarbon cloth (E-TEK, HT 2500-W) and dried at 190° C. in a conventionaloven. Hot-pressing was performed at 130° C. applying a load of 50 kg/cm²for 5 min. In this example, the MEA of Nafion 117 membrane wasfabricated by following procedure: Pt—C was mixed with deionized water,isopropyl alcohol (Sigma-Aldrich) and Nafion solution (5 wt % solution,EW1000, Dupont) to form a catalyst ink. The catalyst ink was paintedonto carbon cloth (E-TEK, HT 2500-W) and dried at 80 and 120° C. for 40and 60 min respectively in a conventional oven. The MEA was made byhot-pressing a sandwich of electrodes and a Nafion 117 membrane at 140°C. for 3 min with a pressure of 50 kg/cm². Prior to the i-V measurement,the MEAs of composite membranes and Nafion 117 were activated.

FIGS. 16A-16C show polarization curves of SBA₁₁-PPDC₃₄ and SBA₉-PPMC₆₃composite membranes in the temperature range of 80-180° C. and FIG.16D-16F show polarization curves of SBA₉-PPDC₆₄ and SBA₇-PPMC₄₃composite membranes in the temperature range of 80-180° C.

Referring to FIG. 16A, polarization curves of SBA₁₁-PPDC₃₄ andSBA₉-PPMC₆₃ composite membranes along with PA-PBI membrane at 80° C. areshown in chart 1601, and polarization curves of SBA₁₁-PPDC₃₄ andSBA₉-PPMC₆₃ composite membranes along with PA-PBI membrane at 90° C. areshown in chart 1602. In FIG. 16B, polarization curves of SBA₁₁-PPDC₃₄and SBA₉-PPMC₆₃ composite membranes along with PA-PBI membrane at 100°C. are shown in chart 1603, and polarization curves of SBA₁₁-PPDC₃₄ andSBA₉-PPMC₆₃ composite membranes along with PA-PBI membrane at 120° C.are shown in chart 1604. In FIG. 16C polarization curves of SBA₁₁-PPDC₃₄and SBA₉-PPMC₆₃ composite membranes along with PA-PBI membrane at 150°C. are shown in chart 1605, and polarization curves of SBA₁₁-PPDC₃₄ andSBA₉-PPMC₆₃ composite membranes along with PA-PBI membrane at 180° C.are shown in chart 1606. In this example, the anode and cathode Ptloadings were both 0.5 mg/cm². Each MEA with an active area of 2.3×2.3cm² underwent the fuel cell test with the H₂/O₂ flow rates at 300/500mL/min under anhydrous condition.

Referring to FIG. 16D, polarization curves of SBA₉-PPDC₆₄ andSBA₇-PPMC₄₃ composite membranes along with PA-PBI membrane at 80° C. areshown in chart 1607, and polarization curves of SBA₉-PPDC₆₄ andSBA₇-PPMC₄₃ composite membranes along with PA-PBI membrane at 90° C. areshown in chart 1608. In FIG. 16E, polarization curves of SBA₉-PPDC₆₄ andSBA₇-PPMC₄₃ composite membranes along with PA-PBI membrane at 100° C.are shown in chart 1609, and polarization curves of SBA₉-PPDC₆₄ andSBA₇-PPMC₄₃ composite membranes along with PA-PBI membrane at 120° C.are shown in chart 1610. In FIG. 16F polarization curves of SBA₉-PPDC₆₄and SBA₇-PPMC₄₃ composite membranes along with PA-PBI membrane at 150°C. are shown in chart 1611, and polarization curves of SBA₉-PPDC₆₄ andSBA₇-PPMC₄₃ composite membranes along with PA-PBI membrane at 180° C.are shown in chart 1612. In this example, the anode and cathode Ptloadings were both 0.5 mg/cm². Each MEA with an active area of 2.3×2.3cm² was performed the fuel cell test with the H₂/O₂ flow rates at300/500 mL/min under anhydrous condition.

With further reference to FIGS. 16A-16F, SBA₁₁-PPDC₃₄ and SBA₉-PPDC₆₄composite membranes displayed high fuel cell performance compared withSBA₉-PPMC₆₃ and SBA₇-PPMC₄₃ composite membranes due to high protonconductivity. The fuel cell performance of composite membrane increasesas the temperature was increased from 80° C. to 180° C. The cause ofthis phenomenon is high proton conductivity and reaction kinetics ofcomposite membranes at high temperatures. OCV value of compositemembranes increased with increasing temperature as a result ofconfirmation of the applicability of these membranes at hightemperatures.

In Table 3 below, fuel cell performance parameters for compositemembranes at 180° C. and 0.5 V are presented. The SBA₁₁-PPDC₃₄ compositemembranes showed the highest fuel cell performance. Several factors cancontribute to the high fuel cell performance SBA₁₁-PPDC₃₄ compositemembranes, such as high proton conductivity, suitable surface roughness,uniform and high level of SBA-15-Ph-SO₃H mesoporous, pores ofSBA-15-Ph-SO₃H mesoporous, hydrogen interactions of -Ph-SO₃H groups withionic liquids and high proton conductivity life time. Current densityfor SBA₁₁-PPDC₃₄ composite membranes at 0.5 V and 80° C. was 0.22 A/cm²(chart 1601). This current density was increased to about 1.16 A/cm² at180° C. (chart 1606).

TABLE 3 Fuel cell parameters of composite membranes at 180° C. and 0.5V. SBA₇- SBA₉- SBA₉- SBA₁₁- Membrane PPMC₄₃ PPDC₆₄ PPMC₆₃ PPDC₃₄ Currentdensity 0.65 0.91 0.72 1.16 (A/cm²) Power density 0.32 0.45 0.36 0.58(W/cm²)

FIG. 17 shows polarization curves for Nafion 117 membrane at 80° C., 90°C., 100° C. and 120° C. The anode and cathode Pt loadings were both 0.5mg/cm². The active area of each MEA was 2.3×2.3 cm². The performance ofNafion 117 is noticeably decreased with increasing temperature from 80°C. to 120° C. This occurs because of the requirement of humidificationof Nafion 117 for a good operation. As the relative humidity decreasesat higher temperatures, the performance of Nafion 117 MEA would alsodecrease. FIG. 17 shows that the OCV drops from 0.98 V at 80° C. to avalue of only 0.51 V at 120° C. Polarization curves for Nafion 117 at150° C. and 180° C. could not be obtained due to the absence ofmoisture. Referring to FIG. 17, the power density of Nafion 117decreases with increases in temperature due to decreasing relativehumidity. However, the power density of PA-PBI, dicationic membranes,monocationic membranes, dicationic and monocationic composite membranesincrease with increasing temperature.

FIG. 18A shows power density plots of PPDC₃₄, PPMC₆₃, SBA₁₁-PPDC₃₄,SBA₉-PPMC₆₃ composite membranes along with power density plots of Nafionand PA-PBI at 0.5 V. FIG. 18B shows power density plots of PPDC₆₄,PPMC₄₃, SBA₉-PPDC₆₄, SBA₇-PPMC₄₃ composite membranes along with powerdensity plots of Nafion and PA-PBI at 0.5 V. Referring to FIGS. 18A and18B, a similar trend of increase in the monocationic composite membranes(SBA₉-PPMC₆₃ and SBA₇-PPMC₄₃) compared to monocationic membranes (PPMC₆₃and PPMC₄₃) is observed. This observation is due to the presence ofSBA-15-Ph-SO₃H mesoporous in the structure of composite membranes.SBA-15-Ph-SO₃H mesoporous keep ionic liquids and PA in the structure ofthe composite membranes due to strong and effective hydrogeninteraction. In other words SBA-15-Ph-SO₃H mesoporous reduces PA andionic liquids leaching and to be climbing onto the power density. TheSBA₁₁-PPDC₃₄ dicationic composite membranes displayed power density of0.58 W/cm² at 180° C. and 0.5 V. These results indicate that thecapability of SBA₁₁-PPDC₃₄ dicationic composite membranes to providehigh fuel cell performance for use in high temperature PEM fuel cells.

FIG. 19A shows a life test result of a PPDC₃₄ membrane unit celloperated at 180° C. under a constant current loading of 0.4 A/cm² andFIG. 19B shows a life test result of a SBA₁₁-PPDC₃₄ membrane unit celloperated at 180° C. under a constant current loading of 0.4 A/cm² Duringeach 24-hour cycle the life test was interrupted (12 times), includingfour complete shut downs after each sixty hours after the test started.Under a fixed loading current for a long time fuel cell test, tworegions were observed in the output voltage versus testing time curve.The first initial testing period was the “activation region” in whichcell voltage increased with operating time. The improvement of fuel cellperformance at the “activation region” is due to the better contact ofmembrane with catalyst layers by the pressure of the end plates andexpansion of the interface for the electrochemical reaction. Followingthe “activation region” was the “decline region”, in which the cellvoltage decreased with operating time. The decline of cell voltageduring the latter stage of life test of PPDC₃₄ membranes was due to theleaching of DC₃ ionic liquid and PA from membrane.

Referring to FIG. 19B, it can be seen that a significant increase wasobserved in fuel cell life time of SBA₁₁-PPDC₃₄ composite membranescompared to PPDC₃₄ membranes. Due to retention of PA and DC₃ ionicliquid, SBA-15-Ph-SO₃H mesoporous increases fuel cell life time ofSBA₁₁-PPDC₃₄ composite membranes. OCV value SBA₁₁-PPDC₃₄ compositemembranes remained relatively constant over 150 hours and did notdecrease. These results reflect the successful preparation ofSBA₁₁-PPDC₃₄ composite membranes with high fuel cell performance whichis suitable for applications in high temperature PEM fuel cells.

The well-ordered pores of acid functionalized SBA-15-Ph-SO₃H mesoporousprovide a continuous proton transfer pathway which act as diffusionalbarriers to prevent the dicationic ionic liquid leaching from hightemperature PBI composite membranes, thereby providing high fuel cellperformance.

While the foregoing has described what are considered to be the bestmode and/or other examples, it is understood that various modificationsmay be made therein and that the subject matter disclosed herein may beimplemented in various forms and examples, and that the teachings may beapplied in numerous applications, only some of which have been describedherein. It is intended by the following claims to claim any and allapplications, modifications and variations that fall within the truescope of the present teachings.

Unless otherwise stated, all measurements, values, ratings, positions,magnitudes, sizes, and other specifications that are set forth in thisspecification, including in the claims that follow, are approximate, notexact. They are intended to have a reasonable range that is consistentwith the functions to which they relate and with what is customary inthe art to which they pertain.

The scope of protection is limited solely by the claims that now follow.That scope is intended and should be interpreted to be as broad as isconsistent with the ordinary meaning of the language that is used in theclaims when interpreted in light of this specification and theprosecution history that follows and to encompass all structural andfunctional equivalents.

Notwithstanding, none of the claims are intended to embrace subjectmatter that fails to satisfy the requirement of Sections 101, 102, or103 of the Patent Act, nor should they be interpreted in such a way. Anyunintended embracement of such subject matter is hereby disclaimed.

Except as stated immediately above, nothing that has been stated orillustrated is intended or should be interpreted to cause a dedicationof any component, step, feature, object, benefit, advantage, orequivalent to the public, regardless of whether it is or is not recitedin the claims.

It will be understood that the terms and expressions used herein havethe ordinary meaning as is accorded to such terms and expressions withrespect to their corresponding respective areas of inquiry and studyexcept where specific meanings have otherwise been set forth herein.Relational terms such as first and second and the like may be usedsolely to distinguish one entity or action from another withoutnecessarily requiring or implying any actual such relationship or orderbetween such entities or actions. The terms “comprises,” “comprising,”or any other variation thereof, are intended to cover a non-exclusiveinclusion, such that a process, method, article, or apparatus thatcomprises a list of elements does not include only those elements butmay include other elements not expressly listed or inherent to suchprocess, method, article, or apparatus. An element proceeded by “a” or“an” does not, without further constraints, preclude the existence ofadditional identical elements in the process, method, article, orapparatus that comprises the element.

The Abstract of the Disclosure is provided to allow the reader toquickly ascertain the nature of the technical disclosure. It issubmitted with the understanding that it will not be used to interpretor limit the scope or meaning of the claims. In addition, in theforegoing Detailed Description, it can be seen that various features aregrouped together in various implementations. This is for purposes ofstreamlining the disclosure, and is not to be interpreted as reflectingan intention that the claimed implementations require more features thanare expressly recited in each claim. Rather, as the following claimsreflect, inventive subject matter lies in less than all features of asingle disclosed implementation. Thus, the following claims are herebyincorporated into the Detailed Description, with each claim standing onits own as a separately claimed subject matter.

While various implementations have been described, the description isintended to be exemplary, rather than limiting and it will be apparentto those of ordinary skill in the art that many more implementations andimplementations are possible that are within the scope of theimplementations. Although many possible combinations of features areshown in the accompanying figures and discussed in this detaileddescription, many other combinations of the disclosed features arepossible. Any feature of any implementation may be used in combinationwith or substituted for any other feature or element in any otherimplementation unless specifically restricted. Therefore, it will beunderstood that any of the features shown and/or discussed in thepresent disclosure may be implemented together in any suitablecombination. Accordingly, the implementations are not to be restrictedexcept in light of the attached claims and their equivalents. Also,various modifications and changes may be made within the scope of theattached claims.

What is claimed is:
 1. A proton exchange composite membrane, comprising:a polybenzimidazole (PBI) membrane doped with an acid; animidazolium-based dicationic ionic liquid, wherein a molar ratio of thePBI to the imidazolium-based dicationic ionic liquid is between 2:1 and9:1; and a mesoporous material present at an amount ranging between 5and 15 percent of a total weight of the PBI.
 2. The proton exchangecomposite membrane of claim 1, wherein the imidazolium-based dicationicionic liquid includes anions selected from the group consisting ofCH₃CO₂, CH₃ SO₄, C(CF₃SO₂)₂, (Tf₂N) N(CF₃SO₂)₂, (TfO) CF₃SO₂, BF₄, PF₆,ASF₆, SbF₆, CF₃CO₂, and AlCl₄.
 3. The proton exchange composite membraneof claim 1, wherein the imidazolium-based dicationic ionic liquid isselected from the group consisting of 1,3-di(3-methylimidazolium)propane bis (trifluoromethylsulfonyl) imide, 1,6-di(3-methylimidazolium)hexane bis (hexafluorophosphate), 1,5 bis (3-benzyl-2-methyimidazolium)pentane di-bis (trifloromethanesulfonyl) imide, 1,5 bis(3-methyl-2-phenylimidazolium) pentane di-bis (trifloromethanesulfonyl)imide, 1,5 bis (2,3-dimethylimidazolium) pentane di-bis(trifloromethanesulfonyl) imide, 1,10 bis (2,3-methylimidazolium) decanedi-bis (trifluoromethanesulfonyl) imide, 1,10 bis(2,3-dimethylimidazolium) decane di-bis (trifluoromethanesulfonyl) imideand combinations thereof.
 4. The proton exchange composite membrane ofclaim 1, wherein the imidazolium-based dicationic ionic liquid isselected from the group consisting of 1,3-di(3-methylimidazolium)propane bis (trifluoromethylsulfonyl) imide, 1,6-di(3-methylimidazolium)hexane bis (hexafluorophosphate), and combinations thereof.
 5. Theproton exchange composite membrane of claim 1, wherein the mesoporousmaterial is selected from the group consisting of SBA-15, SBA-16,MCM-41, and MCM-48.
 6. The proton exchange composite membrane of claim1, wherein the mesoporous material is selected from the group consistingof mesoporous SBA-15 silica sulfonic acid and mesoporous SBA-15 silicaphenyl sulfonic acid.
 7. The proton exchange composite membrane of claim1, wherein the acid includes phosphoric acid.
 8. The proton exchangecomposite membrane of claim 1, wherein the proton exchange compositemembrane has an activation energy ranging between 14 and 21 kJ.
 9. Theproton exchange composite membrane of claim 1, wherein a tensilestrength of the proton exchange composite membrane ranges betweenapproximately 18 and 34 MPa.
 10. The proton exchange composite membraneof claim 1, wherein a current density of the proton exchange compositemembrane ranges between approximately 0.6 and 1.2 A/cm² at 0.5 V and180° C.
 11. The proton exchange composite membrane of claim 1, wherein apower density of the proton exchange composite membrane ranges betweenapproximately 0.3 and 0.6 W/cm² at 0.5 V and 180° C.
 12. A method forsynthesizing a proton exchange composite membrane, the methodcomprising: preparing a PBI solution by dissolving PBI powder in asolvent; adding an imidazolium-based dicationic ionic liquid to the PBIsolution to obtain a second solution, wherein a molar ratio of the PBIto the imidazolium-based dicationic ionic liquid is between 2:1 and 9:1;dispersing a mesoporous material in the second solution to obtain athird solution, wherein the mesoporous material is present at an amountranging between 5 and 15 percent of a total weight of the PBI; castingthe third solution; removing a solvent from the third solution to obtaina composite membrane; and doping the composite membrane with an acid.13. The method of claim 12, wherein the imidazolium-based dicationicionic liquid includes anions selected from the group consisting ofCH₃CO₂, CH₃SO₄, C(CF₃SO₂)₂, (Tf₂N) N(CF₃SO₂)₂, (TfO) CF₃SO₂, BF₄, PF₆,ASF₆, SbF₆, CF₃CO₂, and AlCl₄.
 14. The method of claim 12, wherein theimidazolium-based dicationic ionic liquid is selected from the groupconsisting of 1,3-di(3-methylimidazolium) propane bis(trifluoromethylsulfonyl) imide, 1,6-di(3-methylimidazolium) hexane bis(hexafluorophosphate), 1,5 bis (3-benzyl-2-methyimidazolium) pentanedi-bis (trifloromethanesulfonyl) imide, 1,5 bis(3-methyl-2-phenylimidazolium) pentane di-bis (trifloromethanesulfonyl)imide, 1,5 bis (2,3-dimethylimidazolium) pentane di-bis(trifloromethanesulfonyl) imide, 1,10 bis (2,3-methylimidazolium) decanedi-bis (trifluoromethanesulfonyl) imide, 1,10 bis(2,3-dimethylimidazolium) decane di-bis (trifluoromethanesulfonyl) imideand combinations thereof.
 15. The method of claim 12, wherein theimidazolium-based dicationic ionic liquid is selected from the groupconsisting of 1,3-di(3-methylimidazolium) propane bis(trifluoromethylsulfonyl) imide, 1,6-di(3-methylimidazolium) hexane bis(hexafluorophosphate), and combinations thereof.
 16. The method of claim12, wherein the mesoporous material is selected from the groupconsisting of SBA-15, SBA-16, MCM-41, and MCM-48.
 17. The method ofclaim 12, wherein the mesoporous material is selected from the groupconsisting of mesoporous SBA-15 silica sulfonic acid and mesoporousSBA-15 silica phenyl sulfonic acid.
 18. The method of claim 12, whereindoping the composite membrane includes using a phosphoric acid.
 19. Themethod of claim 18, wherein the composite membrane is doped withphosphoric acid at a concentration of 85 wt % over approximately 5 days.20. The method of claim 18, wherein the casting the third solutionincludes casting onto glass plates by a film applicator.